Unsulphonated azo-dyestuff and process of making same



Patented Apr. 30, 1935 UNITED srArss PATENT OFFICE UNSULPHONATED AZO-DYESTUFF AND PROCESS OF MAKING SAME Gerald Bcnhte, Basel, and Max Schmid, Riehen, near Basel, Switzerland, assignors to the firm of Society of Chemical Industry in Basle, Basel,

Switzerland No Drawing. Application January 9, 1934, Serial No. 705,954. In Switzerland Januarylfi, 1933 7 Claims.

CHz-group capable of coupling. The -.CO--] CH2'group may be in an open chain, but it may also be a member of a ring. Such arylides are, for example, the following compounds:-

group, with'a diazotized ortho-aminocarboxylic acid or an ester thereof.

Greenish yellow to orange dyestuffs are thus produced. "They correspond very probably to the general formula [R1-N=N 1 2R2 wherein R1 represents any aromatic radical substituted in ortho-position to the -N=N--group by a COO-alkyl group and R2 the radical of an arylide of a carboxylic acid containing twice a 1 COCII2group capable of coupling. When produced on the fibre the new dyestuffs yield greenish-yellow to orange dyeings which are of extraordinary brightness and depth and have excellent properties of iastness, especially to washing, chlorine and soda boil, which is remarkable in view of the presence of the carboxylic acid ester group which is easily saponified to the carboxylgroup. Moreover, the dyeings which are produced by dyestuffs made from diazotized esters of ortho-aminocarboxylic acid are characterized by fastness to light. These results are the more noteworthy because the dyestuffs which are obtained from the corresponding paraor metaaminocarboxylic acids or their esters are far from having the fastness of those from the orthoderivatives. I U

The arylides of the carboxylic acids capable of coupling which act here as coupling components and contain twice the --CO-Cl-Iz-group capable of coupling may not only comprise arylides from 1 mole of a diamine and 2 moles of a monocarboxylic acid containing only once the -CO CHzgroup capable of coupling, but also arylides from 2 moles of a mono-amine and 1 mole of a dicarboxylic acid containing twice the CO wherein R stands for alkyl, such as methyl or ethyl or for aralkyl or for aryl; further wherein R stands for an aryl radical of the benzene or naphthalene series. These are compounds in which the COCH2--group is in an open chain. In compounds such as the CO--CH2--group lies in a ring.

In the group COO-alkyl of the diazotizing component the alkyl may not only consist of one or two C-atoms, but also of a higher alkyl radical, such as propyl, isobutyl, amyl, capryl, decyl, cetyl, etc. The alkyl group may also be substituted by substituents, such as halogen, OH, OCH3.

The new dyestuffs are useful for producing valuable lakes or pigments, if desired with the aid of substrata or after they have been converted into complex metal compounds, such as copper or chromium compounds.

The following examples illustrate the invention the parts being by weight, unless otherwise stated:-

Example 1 33 parts of 2-aminobenzoio acid-ethyl ester are diazotized in the usual manner. The clear diazosolution thus obtained is poured into a solution consisting of 59.2 parts of the condensation product from 2 moles of 1-(3'carboxyphenyl) -3- methyl-5-pyrazolone and 1 mole of 4,4=diaminodiphenyl, 30 parts of caustic soda solution of 30 per cent. strength, 25 parts of calcined sodium carbonate and 2000 parts of water. The dyestuff thus formed is immediately precipitated. The yellow precipitate is filtered and dried. The new dyestuff corresponds probably to the formula Example 3 Cotton yarn is impregnated with a grounding liquor made by dissolving 3 grams of diacetacetylortho, ortho-tolidine in 300 cc. of hot water with addition of 10 cc. of caustic soda solution of 30 per cent. strength, 10 cc. of Turkey red oil and l t grams of sodium chloride and diluting the whole to 1 litre. The goods are then wrung out and developed in a diazo-solution which has been neutralized with sodium acetate andcontalns the CH3C=N /N=C-CH3 \0 H I N=N 0 COOCzHs COOCzHs Example?! equivalent of 2 grams of Z-aminobenzoic acid- Cotton yarn is impregnated with a grounding liquor made by dissolving 3 grams of diacetacetylortho, ortho'-tolidine in 300 cc. of hot water with addition of 10 cc. of caustic soda solution of 30 ethyl ester per litre. There is produced a dull, pure greenish yellow tint of very good fastness to light and to keir boiling. The new dyestuff corresponds probably to the formula per cent. strength, 10 cc. of Turkey red oil and 14 grams of sodium chloride and the whole diluted to 1 litre. The goods are then wrung out and developed in a diazo-solution neutralized by means of sodium bicarbonate and equivalent to 2 grams of 5-chloro-2-aminobenzoic acid per litre. There is produced a pure greenish-yellow of very good fastness to washing, chlorine and keir boiling. The new dyestufi corresponds probably to the formula OH: H

OOOOIHE COOUQHI Example 4 The material to be printed is foularded with an alkaline'solution which contains per litre 12 grams of dibenzoylacetyl-ortho, ortho'-tolidine.

After drying, the material is printed with a printing color which contains per kilo 8 grams of the diazotized methyl ester of 2-amino-5-chlor0-1- benzoic acid. The pure yellow dyeing develops N I N H CH3 OH: H N r --00 on o0 0H Redder tints are obtained by substituting the benzidide of the 1-(3'-carboxyphenyl)-3 methyl- 5-pyrazolone for the diacetacetyl-ortho, ortho tolidine.

t (1H on f N a a 13 I G O 0 CH3 0 O O CH;

very quickly and is notably fast. The new dyestuff corresponds probably to the formula The following table comprises a number of other dyest'ufis which are obtainable in accordance with this invention:

3. The unsulphonated azo-dyestuffs of the gen? eral formula 3 4 Li k Color tint of the No." Diazo-component Conplmg component combination produced on cotton 1 5-chloro-2-amino-benzoic acid-methyl ester Diacetacetyl-ortho, b 0-t e Greenish-yellow. 2 4-chloro-2-amino-benzoic acid-methyl ester do Yellow. 3 2'an1in0benzoic acid-methyl ester do Reddish-yellow. 10 4 2-ann'nobenzoic acid-ethyl ester Dibenzoylacetyl-ortho, 01't 0-t0l1dine Red yellow. 5 2-amino-5-chloro-benz0ic acid-methyl ester ;do o. 6 2-amino 4-chloro-benzoic acid-ethyl ester do Orange. 7 2-amino-4-chloro benzoic acid-methyl ester- Dibenzoylacetyl-ortho, 0rtho-tolidine Do. 8 2-a1'ninobenzoic acid-ethyl ester Terephthaloyl-bis-acetyl-1-amino-4-metl1y1benzene. Green yellow. 9 2-amino-4-chloro-benzoic acid ethyl ester "do- Do. 10 Z-aminobenzoic acid-ethyl ester Terephtha1oyl-bis-acetyl-l-ammo-l-methoxybenzene. Do. ll iaminol-chlormbenzoic acid-ethyl ester do Yellow. 12 2-aminobenzoic acid-ethyl ester Terephthaloyl-bis-acetyl-1-amin0-2-methoxy-5- Green yellow.

methyl-benzene. 13 2-arnino-5-chloro-benzoic acid-methyl ester do Yellow. 14 2-amino-4-chloro-benzoic acid-ethyl estor.-. do Green yellow. 15 2-aminobenzoic acid-ethyl ester Terephthaloyl-bis-acetyl-Z-amino-naphthalen Yellow. 16 2-amino4-cl1loro-benzoic acid-ethyl ester... d0 D0. 17 2-amin0-5-chloro-benzoic acid-methyl ester '1erephthaloyl-bis-acetylJemima-naphthalene... Red yellow. 18 2-aminobenzoic acid-ethyl ester Terephtha1oyl-bis-acetyl-l-aminoi-chlorobenzen Green yellow. 19 2-amino-4-chloro-benzoic acid-ethyl ester Terephthaloyl-bis-acetyl-l-amino-4-ethoxybenzene Yellow. 20 2aminobenzoic acid-ethyl ester Terephtha1oyl-bis-acetyl-l-amino-Z,4dimethoxy-5- Do.

chlorobenzene.

/ I Dyestufi 14 corresponds to the following wherein R1 represents any aromatlc radical of the formula benzene series substituted in ortho-position to the v QNHCO(l3H-0C-G O(\JHG 0-NH N N OCH: OCH;

N N I CO0C:Ha COOCzHs What we claim is: N=Ngroup by a COG-alkyl group, and R2 1. The unsulphonated azo-dyestufis of the genrepresents the radical of an arylide of a careral formula boxylic acid containing twice the COCH2 group capable of coupling in an open chain, which wherein R1 represents any aromatic radical of products, when produced on the fibre, dye the the benzene or naphthalene series substituted same vivid greenish-yellow to orange tint of 1n ortho-position to the N=Ngr0up by a cellent fastness to soda boil. C ll y} r u and R2 r pr s t e radlgal 4. The unsulphonated azodyestuffs of the genof an arylide of a carboxylic acid. containing twice eral formula the -CO-CH2group capable of couplmg, which products, when produced on the fibre, dye the [R1 N:N ]2 R2 same vivid greenish-yellow to orange tints of 7 excellent fastness to soda boil.

The unsulphonated azmdyestuffs of the gem wherein R1 represents any aromatic radical of the eral formula benzene series substituted in ortho-position to n the N=Ngroup by a COO-alkyl group, the 1 all: 0 t i wherein R1 represents any aromatic radical of the 5 zg g f fi R benzene series substituted in ortho-position to the an 2 n s 0 an ary 1 e 0 by a coo alkyl group and R2 carboxylic acid containing twice the CO--CH2 resents the radical of an arylide of a carboxylic group Capable of Coupllng n an open cha1n,wh1ch 6U acid containing twice the -COCH2-gIOU.p C products, when produced on the fibre, dye the pable of coupling, which products, when produced same vlvld greemsh-yellow to yellow s of on the fibre, dye the same vivid greenish-yellow cellent fastness 0 a 1 0 to orange tints of excellent fastness to soda boil. The a Y Stuff 0f the fo mula CHz-C0-?H-CONHQQNHCO?HCO-CH3 N N H CH; OH: H N N r COOCaHs COOClHI which product, when produced on the fibre, dyes whlch product when Produced on fibre dyes the same fast yellow tints of particular Iastness the same fast yellow tlnts of particular fastness to light chlorine and Soda boil light chlm'ine and soda 7. The azo-dyestuff of the formula 5 1 OH; CH; 5 p ONHCO-(IEHOC-OCO?HCONHQ \OCH fi OCH ,10 z 3 N N 6. The azo-dyestufi of the formula V which product, when preduced on the fibre, dyes,

N l N 20,

1] CH1 OH: H N f the same fast yellow tints of particular fastness to t h light, chlorine and soda, boil. Y 30 GERALD BONHO'IE. I MAX SCHMIDL- i 

